CN109012726A - A kind of molten salt method production of modification by copolymerization carbonitride/zinc oxide composite visible light catalyst and application - Google Patents
A kind of molten salt method production of modification by copolymerization carbonitride/zinc oxide composite visible light catalyst and application Download PDFInfo
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- CN109012726A CN109012726A CN201810825291.6A CN201810825291A CN109012726A CN 109012726 A CN109012726 A CN 109012726A CN 201810825291 A CN201810825291 A CN 201810825291A CN 109012726 A CN109012726 A CN 109012726A
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- carbonitride
- visible light
- zinc oxide
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 238000012986 modification Methods 0.000 title claims abstract description 48
- 230000004048 modification Effects 0.000 title claims abstract description 48
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 47
- 150000003839 salts Chemical class 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 30
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000001103 potassium chloride Substances 0.000 claims abstract description 14
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000007146 photocatalysis Methods 0.000 claims abstract description 10
- 230000001699 photocatalysis Effects 0.000 claims abstract description 10
- 239000011592 zinc chloride Substances 0.000 claims abstract description 7
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000008247 solid mixture Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- -1 dicyanodiamine Chemical compound 0.000 claims description 3
- JTTIOYHBNXDJOD-UHFFFAOYSA-N 2,4,6-triaminopyrimidine Chemical group NC1=CC(N)=NC(N)=N1 JTTIOYHBNXDJOD-UHFFFAOYSA-N 0.000 claims description 2
- AUFJTVGCSJNQIF-UHFFFAOYSA-N 2-Amino-4,6-dihydroxypyrimidine Chemical compound NC1=NC(O)=CC(=O)N1 AUFJTVGCSJNQIF-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- LNDZXOWGUAIUBG-UHFFFAOYSA-N 6-aminouracil Chemical compound NC1=CC(=O)NC(=O)N1 LNDZXOWGUAIUBG-UHFFFAOYSA-N 0.000 claims 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 239000011941 photocatalyst Substances 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000006303 photolysis reaction Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 229910002804 graphite Inorganic materials 0.000 abstract description 2
- 239000010439 graphite Substances 0.000 abstract description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001912 cyanamides Chemical class 0.000 abstract 1
- 238000011033 desalting Methods 0.000 abstract 1
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- 238000013508 migration Methods 0.000 abstract 1
- 230000005012 migration Effects 0.000 abstract 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 11
- 239000004570 mortar (masonry) Substances 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- 229910002090 carbon oxide Inorganic materials 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- IYALFASAICOWQU-UHFFFAOYSA-L dichlorozinc;pyridine Chemical compound [Cl-].[Cl-].[Zn+2].C1=CC=NC=C1 IYALFASAICOWQU-UHFFFAOYSA-L 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- LMHNVTCPELKRSC-UHFFFAOYSA-L zinc pyrimidine dichloride Chemical compound [Cl-].[Cl-].[Zn+2].C1=CN=CN=C1 LMHNVTCPELKRSC-UHFFFAOYSA-L 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011218 binary composite Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical class NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to material preparation and photocatalysis technology fields, are related to molten salt method production and the application of a kind of modification by copolymerization carbonitride/zinc oxide composite visible light catalyst.The composite visible light catalyst is using nitrogenous compounds such as cyanamides as presoma, using different organic micromolecule compounds as comonomer, using the mixture of potassium chloride and zinc chloride as fused-salt medium, is made by a step high-temperature calcination and water-washing desalting.Modification by copolymerization carbonitride/zinc oxide composite visible light catalyst of the invention is nanoscale thin slice, has biggish specific surface area.Compared with carbonitride/zinc oxide composite photocatalyst and traditional graphite phase carbon nitride, the absorption to visible light is enhanced, promotes the separation and migration in light induced electron and hole, improves the photodissociation aquatic products hydrogen activity under visible light.
Description
Technical field
The present invention relates to material preparation and photocatalysis technology field more particularly to a kind of modification by copolymerization carbonitride/zinc oxide
Composite visible light catalyst.
Background technique
Be using sunlight hydrogen production by water decomposition solve environmental pollution and a kind of most potential desirable route of energy crisis, and
Seek key problem that is stable, being efficiently, with visible light-responded photochemical catalyst this field.In recent years, carbonitride was in light
Excellent performance is shown in terms of solution water hydrogen manufacturing, chemical property is stablized, and forbidden bandwidth (~2.7eV) is that one kind has properly
Visible light-responded polymer semiconductor's catalysis material.In the recent period, using a kind of carbonitride of highly crystalline of molten-salt growth method preparation
It is widely used in photolysis water hydrogen (referring to J.Am.Chem.Soc., 2014,136:1730；Chem.Mater.,2015,27:
8237).Wherein, with KCl/ZnCl2For fused-salt medium can a step prepare carbonitride/zinc oxide heterogeneous junction type composite photo-catalyst
(referring to Chem.Commun., 2016,52:13020).The composite photo-catalyst decomposes aquatic products hydrogen activity under visible light and compares fused salt
The pure carbonitride of method preparation improves 63 times.But this composite photo-catalyst still has distinct disadvantage, such as its absorption spectrum
Range is relatively narrow, causes it more low to the utilization rate of visible light.
The absorption spectrum ranges of above-mentioned binary composite photo-catalyst are expanded by the method for modification by copolymerization, and then it is right to promote its
It can be seen that the research work of light utilization efficiency has not been reported.
Summary of the invention
The purpose of the present invention is to provide a kind of molten-salt growth methods of modification by copolymerization carbonitride/zinc oxide composite visible light catalyst
Preparation method and application.In the present invention, by the presoma of carbonitride from different small organic molecule monomers in KCl/ZnCl2Fused salt
Copolymerization is carried out in medium, is realized the adjustment to azotized carbon nano lamella conjugated structure, is enhanced its absorption to visible light,
The separation and transport efficiency of photo-generated carrier are further promoted, and then promotes the photocatalysis performance of material.
Visible light catalyst crystallinity, biggish specific surface area and wider visible light with higher prepared by the present invention
Response range is able to achieve fast transferring and the separation of photo-generated carrier, multiple compared to existing carbonitride/zinc oxide heterogeneous junction type
Light combination catalyst and traditional graphite phase carbon nitride (g-C3N4), visible photocatalysis water hydrogen production activity is higher.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of molten salt method production of modification by copolymerization carbonitride/zinc oxide composite visible light catalyst comprising following
Step:
1) presoma of carbonitride, small organic molecule monomer are mixed with fused salt, is transferred in crucible after grinding uniformly；
2) crucible for filling said mixture is placed in Muffle furnace, is naturally cooling to room after calcining in air atmosphere
Temperature；
3) solid mixture in crucible is washed with hot water, eliminates salt therein, modification by copolymerization nitridation is obtained after dry
Carbon/zinc oxide composite visible light catalyst.
In the above preparation method, in step 1) carbonitride presoma be selected from melamine (also known as melamine, extract of protein),
Any one or more in dicyanodiamine (also known as cyanoguanidines, cyanamid dimerization), cyanamide (abbreviation cyanamide).
In the above preparation method, small organic molecule monomer is selected from 2,4,6- Triaminopyrimidines, amino -2 4- in step 1),
Any one in 6- dihydroxy-pyrimidine, 2- amino -4,6- dihydroxy-pyrimidine.
In the above preparation method, the mass ratio of the presoma of carbonitride and small organic molecule monomer is 1 in step 1):
0.005~0.25
In the above preparation method, in step 1) fused salt be potassium chloride and zinc chloride mixture, the mass ratio of the two is
1:0.5~1.5.
In preferred embodiments, the presoma of carbonitride, small organic molecule list in the step 1) of above-mentioned preparation method
The mass ratio of body and fused salt is 1:0.05:10.
In the above preparation method, the heating rate calcined in step 2) is 1.5~5 DEG C/min.
In the above preparation method, the temperature calcined in step 2) is 520~600 DEG C.
In the above preparation method, the soaking time calcined in step 2) is 2~8 hours.
In the above preparation method, the temperature of hot water is 60~90 DEG C in step 3).
A kind of carbonitride of the modification by copolymerization as made from above-mentioned preparation method/zinc oxide composite visible light catalyst.
Above-mentioned modification by copolymerization carbonitride/zinc oxide composite visible light catalyst decomposes water under visible light and prepares in hydrogen
Using.
Compared with prior art, by adopting the above technical scheme the present invention has the advantage that
(1) present invention prepares the modified carbonitride composite wood of sheet using molten-salt growth method under the liquid environment of High temperature ion
Material, is heated evenly the presoma of carbonitride, the crystallinity of gained composite photocatalyst material is higher, and specific surface area is bigger；
(2) in the preparation process in accordance with the present invention, the zinc ion in fused salt is contacted with air at high temperature, to be changed into oxygen
Change zinc, therefore zinc chloride is not only used as fused-salt medium, but also as the presoma of the zinc oxide in product, so that preparation process is more simple
It is single convenient；
(3) compared with existing carbonitride/zinc oxide heterogeneous junction type composite photo-catalyst, modification by copolymerization prepared by the present invention
Carbonitride/absorption of the zinc oxide composite visible light catalyst in visible light region is improved, and photoproduction current-carrying is further improved
The separation and transport efficiency of son, and then improve the photocatalysis performance of material；
(4) modification by copolymerization carbonitride/zinc oxide composite visible light catalyst prepared by the present invention, wherein having for modified
Machine small molecule monomer selectivity range is wide, has good Modulatory character and universality；
(5) modification by copolymerization of the invention carbonitride/zinc oxide composite visible light catalyst is efficient, stablizes, in photocatalysis body
It is separated and is reused with can be convenient in system, there is very high practical value and broad application prospect.
Detailed description of the invention
Fig. 1 is modification by copolymerization carbonitride/zinc oxide composite visible light catalyst scanning electron microscope in embodiment 1
(SEM) spectrogram.
Fig. 2 is modification by copolymerization carbonitride/zinc oxide composite visible light catalyst X-ray diffraction (XRD) spectrum in embodiment 1
Figure.
Fig. 3 is modification by copolymerization carbonitride/zinc oxide composite visible light catalyst power spectrum (EDS) spectrogram in embodiment 1.
Fig. 4 is to nitrogenize in modification by copolymerization carbonitride/zinc oxide composite visible light catalyst a and comparative example 1 in embodiment 1
Carbon/zinc oxide composite photocatalyst b ultraviolet-visible diffuse reflectance spectrum (UV-Vis DRS) compares figure.
Fig. 5 be carbonitride in modification by copolymerization carbonitride/zinc oxide composite visible light catalyst and comparative example 1 in embodiment 1/
G-C in zinc oxide composite photocatalyst, comparative example 23N4The performance for carrying out visible light catalytic hydrogen manufacturing compares figure, and wherein a is embodiment
1 modification by copolymerization carbonitride/zinc oxide photocatalysis material, b are carbonitride/zinc oxide photocatalysis material in comparative example 1, and c is
G-C in comparative example 23N4。
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1: molten-salt growth method prepares modification by copolymerization carbonitride/zinc oxide composite visible light catalyst
It is phonetic that 0.05g 2,4,6- triamido is added into the mixture of 1.0g cyanamide, 4.5g potassium chloride and 5.5g zinc chloride
Pyridine.It is transferred to after being ground said mixture in mortar in 50mL crucible.This crucible is placed in Muffle furnace and is calcined: being risen
Warm rate is 2.1 DEG C/min, and 6h is kept the temperature after being warming up to 520 DEG C, is then naturally cooling to room temperature.By the solid mixture in crucible
It is washed with a large amount of hot water (60~90 DEG C), eliminates salt therein, dried in 60 DEG C of baking ovens, obtain modification by copolymerization carbonitride/oxygen
Change zinc composite visible light catalyst (yield 20%).
Gained modification by copolymerization carbonitride/zinc oxide composite visible light catalyst SEM spectrogram is as shown in Figure 1, can by Fig. 1
Know, product morphology is more regular, is nanoscale thin slice.Its XRD spectrum as shown in Fig. 2, from Fig. 2 it can be found that 12.1 °,
Occur three diffraction maximums for belonging to carbonitride (100), (110) and (210) crystal face at 21.0 ° and 32.3 ° respectively.Its EDS spectrum
Figure is as shown in figure 3, from the figure 3, it may be seen that contain tetra- kinds of elements of C, N, Zn, O in product.
Embodiment 2: molten-salt growth method prepares modification by copolymerization carbonitride/zinc oxide composite visible light catalyst
It is phonetic that 0.05g2,4,6- triamido is added into the mixture of 1.0g cyanamide, 4.5g potassium chloride and 5.5g zinc chloride
Pyridine.It is transferred to after being ground said mixture in mortar in 50mL crucible.This crucible is placed in Muffle furnace and is calcined: being risen
Warm rate is 2.1 DEG C/min, and 4h is kept the temperature after being warming up to 520 DEG C, is then naturally cooling to room temperature.By the solid mixture in crucible
It is washed with a large amount of hot water (60~90 DEG C), eliminates salt therein, dried in 60 DEG C of baking ovens, obtain modification by copolymerization carbonitride/oxygen
Change zinc composite visible light catalyst (yield 22%).
Embodiment 3: molten-salt growth method prepares modification by copolymerization carbonitride/zinc oxide composite visible light catalyst
It is phonetic that 0.10g 2,4,6- triamido is added into the mixture of 2.0g cyanamide, 4.5g potassium chloride and 5.5g zinc chloride
Pyridine.It is transferred to after being ground said mixture in mortar in 50mL crucible.This crucible is placed in Muffle furnace and is calcined: being risen
Warm rate is 2.1 DEG C/min, and 6h is kept the temperature after being warming up to 520 DEG C, is then naturally cooling to room temperature.By the solid mixture in crucible
It is washed with a large amount of hot water (60~90 DEG C), eliminates salt therein, dried in 60 DEG C of baking ovens, obtain modification by copolymerization carbonitride/oxygen
Change zinc composite visible light catalyst (yield 24%).
Embodiment 4: molten-salt growth method prepares modification by copolymerization carbonitride/zinc oxide composite visible light catalyst
0.10g 2,4,6- triamido is added into the mixture of 1.0g dicyanodiamine, 4.5g potassium chloride and 5.5g zinc chloride
Pyrimidine.It is transferred to after being ground said mixture in mortar in 50mL crucible.This crucible is placed in Muffle furnace and is calcined:
Heating rate is 2.1 DEG C/min, and 6h is kept the temperature after being warming up to 520 DEG C, is then naturally cooling to room temperature.Solid in crucible is mixed
Object is washed with a large amount of hot water (60~90 DEG C), eliminates salt therein, is dried in 60 DEG C of baking ovens, obtain modification by copolymerization carbonitride/
Zinc oxide composite visible light catalyst (yield 36%).
Embodiment 5: molten-salt growth method prepares modification by copolymerization carbonitride/zinc oxide composite visible light catalyst
0.15g 2,4,6- triamido is added into the mixture of 1.0g melamine, 4.5g potassium chloride and 5.5g zinc chloride
Pyrimidine.It is transferred to after being ground said mixture in mortar in 50mL crucible.This crucible is placed in Muffle furnace and is calcined:
Heating rate is 2.1 DEG C/min, and 6h is kept the temperature after being warming up to 520 DEG C, is then naturally cooling to room temperature.Solid in crucible is mixed
Object is washed with a large amount of hot water (60~90 DEG C), eliminates salt therein, is dried in 60 DEG C of baking ovens, obtain modification by copolymerization carbonitride/
Zinc oxide composite visible light catalyst (yield 56%).
Embodiment 6: molten-salt growth method prepares modification by copolymerization carbonitride/zinc oxide composite visible light catalyst
0.15g 2,4,6- triamido is added into the mixture of 1.0g melamine, 4.5g potassium chloride and 5.5g zinc chloride
Pyrimidine.It is transferred to after being ground said mixture in mortar in 50mL crucible.This crucible is placed in Muffle furnace and is calcined:
Heating rate is 2.1 DEG C/min, and 6h is kept the temperature after being warming up to 550 DEG C, is then naturally cooling to room temperature.Solid in crucible is mixed
Object is washed with a large amount of hot water (60~90 DEG C), eliminates salt therein, is dried in 60 DEG C of baking ovens, obtain modification by copolymerization carbonitride/
Zinc oxide composite visible light catalyst (yield 48%).
Embodiment 7: molten-salt growth method prepares modification by copolymerization carbonitride/zinc oxide composite visible light catalyst
0.05g 4- amino -2,6- two is added into the mixture of 1.0g cyanamide, 4.5g potassium chloride and 5.5g zinc chloride
Hydroxy pyrimidine.It is transferred to after being ground said mixture in mortar in 50mL crucible.This crucible is placed in Muffle furnace
Calcining: heating rate is 2.1 DEG C/min, and 6h is kept the temperature after being warming up to 520 DEG C, is then naturally cooling to room temperature.By consolidating in crucible
Body mixture is washed with a large amount of hot water (60~90 DEG C), eliminates salt therein, is dried in 60 DEG C of baking ovens, is obtained modification by copolymerization nitrogen
Change carbon/zinc oxide composite visible light catalyst (yield 19%).
Embodiment 8: molten-salt growth method prepares modification by copolymerization carbonitride/zinc oxide composite visible light catalyst
0.05g 2- amino -4,6- two is added into the mixture of 1.0g cyanamide, 4.5g potassium chloride and 5.5g zinc chloride
Hydroxy pyrimidine.It is transferred to after being ground said mixture in mortar in 50mL crucible.This crucible is placed in Muffle furnace
Calcining: heating rate is 2.1 DEG C/min, and 6h is kept the temperature after being warming up to 520 DEG C, is then naturally cooling to room temperature.By consolidating in crucible
Body mixture is washed with a large amount of hot water (60~90 DEG C), eliminates salt therein, is dried in 60 DEG C of baking ovens, is obtained modification by copolymerization nitrogen
Change carbon/zinc oxide composite visible light catalyst (yield 22%).
Comparative example 1: carbonitride/zinc oxide composite photocatalyst preparation.
After 1.0g cyanamide, 4.5g potassium chloride and 5.5g zinc chloride being ground in mortar be transferred to 50mL crucible
In.This crucible is placed in Muffle furnace and is calcined: heating rate is 2.1 DEG C/min, and 6h is kept the temperature after being warming up to 520 DEG C, then natural
It is cooled to room temperature.Solid mixture in crucible is washed with a large amount of hot water (60~90 DEG C), eliminates salt therein, is dried in 60 DEG C
It is dried in case, obtains carbonitride/zinc oxide composite photocatalyst (yield 20%).
Fig. 4 is the resulting modification by copolymerization carbonitride/zinc oxide composite visible light catalyst a of embodiment 1 and 1 gained of comparative example
Carbonitride/zinc oxide composite photocatalyst b UV-Vis DRS comparison diagram.As seen from Figure 4, the resulting production of embodiment 1
The absorption belt edge of object is obviously red compared to the resulting carbonitride/zinc oxide composite photocatalyst of comparative example 1 in 470nm or so
It moves, and the catalysis material is remarkably reinforced the absorption of light in the visual field of 400nm~800nm, shows that this modification by copolymerization nitrogenizes
Carbon/zinc oxide composite visible light catalyst can preferably utilize visible light.
Comparative example 2:g-C3N4The preparation of photochemical catalyst.
Cyanamide (2.0g) is placed in 50mL crucible.The crucible is placed in Muffle furnace and is calcined: heating rate 2.1
DEG C/min, 6h is kept the temperature after being warming up to 520 DEG C, is then naturally cooling to room temperature.Obtained solid is finely ground in mortar, obtain g-
C3N4Photochemical catalyst (yield 50%).
Experimental example: the photodissociation aquatic products hydrogen experiment of photochemical catalyst.
It is tested using photolysis water hydrogen system.Modification by copolymerization carbonitride/zinc oxide obtained in embodiment 1 is compound
Visible light catalyst (50mg) is added in the mixed solution of triethanolamine (10mL) and water (90mL), and ultrasound is transferred in a moment
In reactor and H is added2PtCl6(3wt%).In entire test process, remains stirring and connect cooling water, make to react
System is maintained at room temperature.It vacuumizes, with all gas in removing system.Opening light source (300W xenon lamp, optical filter λ >
420nm), light-catalyzed reaction is carried out.Pass through online gas chromatographic analysis technique, the H of measurement reaction generation2, result such as Fig. 5 institute
Show.
As shown in Figure 5, under visible light, modification by copolymerization carbonitride/zinc oxide composite visible light catalystization decomposes water system
Hydrogen rate reaches 60 μm of ol/h, carbonitride/zinc oxide composite photocatalyst (22 μm of ol/h) obtained about in comparative example 1
2.7 times, be tradition g-C obtained in comparative example 23N49.2 times of (6.5 μm of ol/h) illustrate modification by copolymerization nitridation of the invention
Carbon/zinc oxide composite visible light catalyst has higher visible photocatalysis water hydrogen production activity.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (11)
1. a kind of molten salt method production of modification by copolymerization carbonitride/zinc oxide composite visible light catalyst, which is characterized in that its
Include the following steps:
1) presoma of carbonitride, small organic molecule monomer are mixed with fused salt, is transferred in crucible after grinding uniformly；
2) crucible for filling said mixture is placed in Muffle furnace, is naturally cooling to room temperature after calcining in air atmosphere；
3) solid mixture in crucible is washed with hot water, eliminates salt therein, obtains modification by copolymerization carbonitride/oxygen after dry
Change zinc composite visible light catalyst.
2. preparation method according to claim 1, it is characterised in that: in the step 1), the presoma of the carbonitride
Any one or more in melamine, dicyanodiamine, cyanamide.
3. preparation method according to claim 1, it is characterised in that: in the step 1), small organic molecule monomer is selected from
2,4,6- Triaminopyrimidine, 4- amino -2,6- dihydroxy-pyrimidine, any one in 2- amino -4,6- dihydroxy-pyrimidine.
4. preparation method according to claim 1, it is characterised in that: in the step 1), the fused salt be potassium chloride with
The mixture of zinc chloride, wherein the mass ratio of the potassium chloride and the zinc chloride is 1:0.5~1.5.
5. preparation method according to claim 1, it is characterised in that: in the step 1), the presoma of the carbonitride,
The mass ratio of small organic molecule monomer and fused salt is 1:0.005~0.25:2~12.
6. preparation method according to claim 1, it is characterised in that: in the step 2), the heating rate of the calcining
It is 1.5~5 DEG C/min.
7. preparation method according to claim 1, it is characterised in that: in the step 2), the temperature of the calcining is 520
~600 DEG C.
8. preparation method according to claim 1, it is characterised in that: in the step 2), the soaking time of the calcining
It is 2~8 hours.
9. preparation method according to claim 1, it is characterised in that: in the step 3), the temperature of the hot water is 60
~90 DEG C.
10. the carbonitride of modification by copolymerization made from preparation method described in any one of claims 1 to 9/zinc oxide is compound visible
Photochemical catalyst.
11. modification by copolymerization carbonitride described in any one of claim 10/zinc oxide composite visible light catalyst photocatalysis under visible light
Decompose the application in aquatic products hydrogen.
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| CN111044586B (en) * | 2019-11-06 | 2022-03-22 | 江苏大学 | Preparation method of bismuth-doped polymeric carbon nitride nanocomposite material containing carbon defects |
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